US5373080A - Process for producing polycarbodiimide resin - Google Patents

Process for producing polycarbodiimide resin Download PDF

Info

Publication number
US5373080A
US5373080A US08/101,309 US10130993A US5373080A US 5373080 A US5373080 A US 5373080A US 10130993 A US10130993 A US 10130993A US 5373080 A US5373080 A US 5373080A
Authority
US
United States
Prior art keywords
phospholene
polycarbodiimide resin
oxide
resin
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US08/101,309
Inventor
Yasuo Imashiro
Ikuo Takahashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nisshinbo Holdings Inc
Original Assignee
Nisshinbo Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nisshinbo Industries Inc filed Critical Nisshinbo Industries Inc
Assigned to NISSHINBO INDUSTRIES, INC. reassignment NISSHINBO INDUSTRIES, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IMASHIRO, YASUO, TAKAHASHI, IKUO
Application granted granted Critical
Publication of US5373080A publication Critical patent/US5373080A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
    • C08G18/168—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring

Definitions

  • the present invention relates to a process for producing a polycarbodiimide resin. More particularly, the present invention relates to a process for producing a polycarbodiimide resin having good storage stability and excellent miscibility with organic solvents.
  • Polycarbodiimide resins having a structure of --N ⁇ C ⁇ N-- in the molecule are known to have high heat resistance and other excellent properties and are in use in various fields as a thermosetting resin.
  • Polycarbodiimide resins have been produced in a reaction system using a solvent, except for few exceptional cases, because since the reactivity of carbodiimide group is high, carbodiimidization in high degree invites gelling due to the occurrence of side reactions. Consequently, the resulting polycarbodiimide resin has had limited applications owing to the solvent used.
  • a polycarbodiimide resin produced using a high-boiling solvent finds no applications where a low-boiling solvent must be used.
  • the above polycarbodiimide resin may be used in said applications by conducting concentration to remove part or all of the high-boiling solvent and replace it with a low-boiling solvent.
  • concentration to remove part or all of the high-boiling solvent and replace it with a low-boiling solvent.
  • carbodiimide group since the reactivity of carbodiimide group is so high as to invite gelling even in a solution, it is virtually very difficult to remove part or all of the high-boiling solvent.
  • the present invention has been brought about in order to eliminate the above drawbacks of the prior art and provide a process for producing a polycarbodiimide resin having good storage stability and excellent miscibility with organic solvents.
  • a process for producing a polycarbodiimide resin from an aliphatic diisocyanate and a terminal-blocking agent in the presence of a carbodiimidization catalyst wherein the aliphatic diisocyanate is tetramethylxylylene diisocyanate represented by the following formula ##STR2## and polymerization is conducted using no solvent.
  • the aliphatic diisocyanate used in the present invention is tetramethylxylylene diisocyanate represented by the above formula. More specifically, it is exemplified by p-tetramethylxylylene diisocyanate represented by the following formula ##STR3## or m-tetramethylxylylene diisocyanate represented by the following formula.
  • the first feature of the present invention lies in that a polycarbodiimide resin having good storage stability and excellent miscibility with organic solvents is produced by using tetramethylxylylene diisocyanate.
  • the terminal-blocking agent used in the present invention includes, for example, an aliphatic monoisocyanate. It can be exemplified by n-butyl isocyanate, tert-butyl isocyanate, isobutyl isocyanate, ethyl isocyanate, n-propyl isocyanate, isopropyl isocyanate, cyclohexyl isocyanate and n-octadecyl isocyanate. Of these, n-butyl isocyanate is particularly preferable.
  • tetramethylxylylene diisocyanate and the terminal-blocking agent are subjected to a condensation reaction (wherein removal of carbon dioxide takes place) to produce a polycarbodiimide resin.
  • the basic reaction is the same as in the conventional processes for polycarbodiimide resin production [U.S. Pat. No. 2,941,956; Japanese Patent Publication No. 33279/1972; J. Org. Chem., 28,2069-2075 (1963); Chemical Review 1981, vol. 81, No. 4, 619-621].
  • the condensation reaction between tetramethylxylylene diisocyanate and an aliphatic monoisocyanate as terminal-blocking agent proceeds in the presence of a carbodiimidization catalyst.
  • a carbodiimidization catalyst there can be used, for example, phospholeneoxides such as 1-phenyl-2-phospholene-1-oxide, 3- methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2- phospholene1-oxide, 1-ethyl-2-phospholene1-oxide, 3methyl-1-phenyl-2-phospholene-1-oxide and 3-phospholene isomers thereof.
  • 3-methyl-1-phenyl-2-phospholene-1-oxide is preferable in view of the reactivity.
  • an organic solvent has ordinarily been used in the conventional processes for aliphatic polycarbodiimide resin production. In the condensation reaction of the present process, however, no solvent is used, and this is a second feature of the present invention.
  • the temperature of the above condensation reaction is in the range of preferably about 120° C. to about 250° C., more preferably about 150° C. to about 190° C.
  • the amount ratio of tetramethylxylylene diisocyanate to the aliphatic monoisocyanate is preferably in the range of 2:1 to 2:30 (molar ratio). Consequently, the polymerization degree of the resulting polycarbodiimide resin becomes 1 to 30.
  • reaction between tetramethylxylylene diisocyanate and the aliphatic monoisocyanate as terminal-blocking agent is conducted in an inert gas (e.g. nitrogen) current to complete the reaction quickly.
  • an inert gas e.g. nitrogen
  • the polycarbodiimide resin obtained in the present process using no solvent is a viscous liquid resin and has no problem of limited applications seen in polycarbodiimide resins produced by the conventional processes using a solvent. Further, the polycarbodiimide resin obtained in the present process not only has very good storage stability but also is soluble in various organic solvents and can be used in various applications (e.g. crosslinking agent for aqueous resin) by selecting an appropriate solvent suitable for each application.
  • polycarbodiimide resins obtained in Examples 2-7 similarly to the polycarbodiimide resin obtained in Example 1, were soluble in various organic solvents.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention provides a process for producing a polycarbodiimide resin from an aliphatic diisocyanate and a terminal-blocking agent in the presence of a carbodiimidization catalyst, wherein the aliphatic diisocyanate is tetramethylxylylene diisocyanate represented by the following formula ##STR1## and polymerization is conducted using no solvent. The polycarbodiimide resin obtained by the above process has good storage stability and excellent miscibility with organic solvents.

Description

BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention relates to a process for producing a polycarbodiimide resin. More particularly, the present invention relates to a process for producing a polycarbodiimide resin having good storage stability and excellent miscibility with organic solvents.
(2) Description of the Prior Art
Polycarbodiimide resins having a structure of --N═C═N-- in the molecule are known to have high heat resistance and other excellent properties and are in use in various fields as a thermosetting resin.
Polycarbodiimide resins have been produced in a reaction system using a solvent, except for few exceptional cases, because since the reactivity of carbodiimide group is high, carbodiimidization in high degree invites gelling due to the occurrence of side reactions. Consequently, the resulting polycarbodiimide resin has had limited applications owing to the solvent used.
For example, a polycarbodiimide resin produced using a high-boiling solvent finds no applications where a low-boiling solvent must be used.
The above polycarbodiimide resin may be used in said applications by conducting concentration to remove part or all of the high-boiling solvent and replace it with a low-boiling solvent. However, since the reactivity of carbodiimide group is so high as to invite gelling even in a solution, it is virtually very difficult to remove part or all of the high-boiling solvent.
Even if the above problem caused by the use of a solvent in polycarbodiimide production could be solved, problems still exist when the produced polycarbodiimide resin has low storage stability or poor miscibility with organic solvents.
SUMMARY OF THE INVENTION
The present invention has been brought about in order to eliminate the above drawbacks of the prior art and provide a process for producing a polycarbodiimide resin having good storage stability and excellent miscibility with organic solvents.
According to the present invention there is provided a process for producing a polycarbodiimide resin from an aliphatic diisocyanate and a terminal-blocking agent in the presence of a carbodiimidization catalyst, wherein the aliphatic diisocyanate is tetramethylxylylene diisocyanate represented by the following formula ##STR2## and polymerization is conducted using no solvent.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is hereinafter described in detail.
The aliphatic diisocyanate used in the present invention is tetramethylxylylene diisocyanate represented by the above formula. More specifically, it is exemplified by p-tetramethylxylylene diisocyanate represented by the following formula ##STR3## or m-tetramethylxylylene diisocyanate represented by the following formula.
In the present invention, no other aliphatic diisocyanate can be used. That is, the first feature of the present invention lies in that a polycarbodiimide resin having good storage stability and excellent miscibility with organic solvents is produced by using tetramethylxylylene diisocyanate.
The terminal-blocking agent used in the present invention includes, for example, an aliphatic monoisocyanate. It can be exemplified by n-butyl isocyanate, tert-butyl isocyanate, isobutyl isocyanate, ethyl isocyanate, n-propyl isocyanate, isopropyl isocyanate, cyclohexyl isocyanate and n-octadecyl isocyanate. Of these, n-butyl isocyanate is particularly preferable.
In the present process, tetramethylxylylene diisocyanate and the terminal-blocking agent are subjected to a condensation reaction (wherein removal of carbon dioxide takes place) to produce a polycarbodiimide resin. The basic reaction is the same as in the conventional processes for polycarbodiimide resin production [U.S. Pat. No. 2,941,956; Japanese Patent Publication No. 33279/1972; J. Org. Chem., 28,2069-2075 (1963); Chemical Review 1981, vol. 81, No. 4, 619-621].
The condensation reaction between tetramethylxylylene diisocyanate and an aliphatic monoisocyanate as terminal-blocking agent (wherein removal of carbon dioxide takes place) proceeds in the presence of a carbodiimidization catalyst. As said catalyst, there can be used, for example, phospholeneoxides such as 1-phenyl-2-phospholene-1-oxide, 3- methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2- phospholene1-oxide, 1-ethyl-2-phospholene1-oxide, 3methyl-1-phenyl-2-phospholene-1-oxide and 3-phospholene isomers thereof. 3-methyl-1-phenyl-2-phospholene-1-oxide is preferable in view of the reactivity.
As mentioned above, an organic solvent has ordinarily been used in the conventional processes for aliphatic polycarbodiimide resin production. In the condensation reaction of the present process, however, no solvent is used, and this is a second feature of the present invention.
The temperature of the above condensation reaction is in the range of preferably about 120° C. to about 250° C., more preferably about 150° C. to about 190° C.
The amount ratio of tetramethylxylylene diisocyanate to the aliphatic monoisocyanate (terminal-blocking agent) is preferably in the range of 2:1 to 2:30 (molar ratio). Consequently, the polymerization degree of the resulting polycarbodiimide resin becomes 1 to 30.
The reaction between tetramethylxylylene diisocyanate and the aliphatic monoisocyanate as terminal-blocking agent is conducted in an inert gas (e.g. nitrogen) current to complete the reaction quickly.
The polycarbodiimide resin obtained in the present process using no solvent is a viscous liquid resin and has no problem of limited applications seen in polycarbodiimide resins produced by the conventional processes using a solvent. Further, the polycarbodiimide resin obtained in the present process not only has very good storage stability but also is soluble in various organic solvents and can be used in various applications (e.g. crosslinking agent for aqueous resin) by selecting an appropriate solvent suitable for each application.
The present invention is hereinafter described in more detail by way of Examples.
EXAMPLE 1
244 g of m-tetramethylxylylene diisocyanate and 22 g of butyl isocyanate were reacted in the presence of 5.32 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 180° C. for 66 hours to obtain a polycarbodiimide resin (polymerization degree=9). The resin had a stability of more than one month at room temperature, which was excellent.
The solubility of the polycarbodiimide resin in various organic solvents is shown in Table 1.
              TABLE 1                                                     
______________________________________                                    
Solvent                  Solubility                                       
______________________________________                                    
Benzene                  Yes                                              
Toluene                  Yes                                              
Xylene                   Yes                                              
Acetone                  Yes                                              
Methyl ethyl ketone      Yes                                              
Ethyl acetate            Yes                                              
Amyl acetate             Yes                                              
Propylene glycol monomethyl ether acetate                                 
                         Yes                                              
Chloroform               Yes                                              
Carbon tetrachloride     Yes                                              
Methylene chloride       Yes                                              
Trichloroethylene        Yes                                              
Tetrachloroethylene      Yes                                              
Dimethylformamide        Yes                                              
______________________________________
EXAMPLE 2
244 g of m-tetramethylxylylene diisocyanate and 22 g of butyl isocyanate were reacted in the presence of 5.32 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 150° C. for 100 hours to obtain a polycarbodiimide resin (polymerization degree=9). The resin had a stability of more than one month at room temperature, which was excellent.
EXAMPLE 3
244 g of m-tetramethylxylylene diisocyanate and 22 g of butyl isocyanate were reacted in the presence of 5.32 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 170° C. for 103 hours to obtain a polycarbodiimide resin (polymerization degree=9). The resin had a stability of more than one month at room temperature, which was excellent.
EXAMPLE 4
244 g of m-tetramethylxylylene diisocyanate and 22 g of butyl isocyanate were reacted in the presence of 5.32 g of a carbodiimidization catalyst (3-methyl-l-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 190° C. for 77 hours to obtain a polycarbodiimide resin (polymerization degree=9). The resin had a stability of more than one month at room temperature, which was excellent.
EXAMPLE 5
244 g of m-tetramethylxylylene diisocyanate and 66 g of butyl isocyanate were reacted in the presence of 6.2 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 180° C. for 28 hours to obtain a polycarbodiimide resin (polymerization degree=3). The resin had a stability of more than one month at room temperature, which was excellent.
EXAMPLE 6
244 g of m-tetramethylxylylene diisocyanate and 10.4g of butyl isocyanate were reacted in the presence of 5.1 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 180° C. for 126 hours to obtain a polycarbodiimide resin (polymerization degree=19). The resin had a stability of more than one month at room temperature, which was excellent.
EXAMPLE 7
244 g of m-tetramethylxylylene diisocyanate and 6.83g of butyl isocyanate were reacted in the presence of 5.0 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 180° C. for 134 hours to obtain a polycarbodiimide resin (polymerization degree =29). The resin had a stability of more than one month at room temperature, which was excellent.
The polycarbodiimide resins obtained in Examples 2-7, similarly to the polycarbodiimide resin obtained in Example 1, were soluble in various organic solvents.
COMPARATIVE EXAMPLE 1
193.5 g of 4,4'-dicyclohexylmethane diisocyanate and 16.5 g of butyl isocyanate were reacted in the presence of 2.10 g of a carbodiimidization catalyst (3-methyl-1-phenyl2-phospholene-1-oxide) in a nitrogen gas current at 180° C. Gelling occurred in 10 hours and no polycarbodiimide resin was obtained.
COMPARATIVE EXAMPLE 2
181.6 g of isophorone diisocyanate and 18 g of butyl isocyanate were reacted in the presence of 2.0 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a nitrogen gas current at 180° C. Gelling occurred in 3 hours and no polycarbodiimide resin was obtained.

Claims (2)

What is claimed is:
1. A process for producing a polycarbodiimide resin comprising reacting a tetramethylxylylene diisocyanate represented by the following formula ##STR4## with an aliphatic monoisocyanate at a molar ratio of the tetramethylxylylene diisocyanate to the aliphatic monoisocyanate of 2:1 to 2:30 in the presence of a carbodiimidization catalyst selected from the group consisting of phospholeneoxides at a temperature in the range of about 120° C. to about 250° C. and in the absence of a solvent.
2. The process of claim 1, wherein the carbodiimidization catalyst is selected from the group consisting of 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2-phospholene-1-oxide, and 3-phospholene isomers thereof.
US08/101,309 1992-08-10 1993-08-03 Process for producing polycarbodiimide resin Expired - Lifetime US5373080A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP23533192A JP3188959B2 (en) 1992-08-10 1992-08-10 Method for producing polycarbodiimide resin
JP4-235331 1992-08-10

Publications (1)

Publication Number Publication Date
US5373080A true US5373080A (en) 1994-12-13

Family

ID=16984527

Family Applications (1)

Application Number Title Priority Date Filing Date
US08/101,309 Expired - Lifetime US5373080A (en) 1992-08-10 1993-08-03 Process for producing polycarbodiimide resin

Country Status (5)

Country Link
US (1) US5373080A (en)
EP (1) EP0582983B1 (en)
JP (1) JP3188959B2 (en)
CA (1) CA2103625C (en)
DE (1) DE69305282T2 (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0780440A2 (en) 1995-12-22 1997-06-25 Rohm And Haas Company Crosslinkable compositions with an aliphatil polycarbodiimide
US5688875A (en) * 1994-06-10 1997-11-18 Nisshinbo Industries, Inc. Hydrophilic tetramethylxylylenecarbodiimide
US5912290A (en) * 1996-02-06 1999-06-15 Nisshinbo Industries, Inc. Hydrolysis stabilizer for ester group-containing resin
US5925409A (en) * 1997-08-27 1999-07-20 Reichhold, Inc. Resins for lining surfaces
US5958516A (en) * 1994-08-11 1999-09-28 Nisshinbo Industries, Inc. Method for surface treating reinforcing material with aqueous carbodiimide containing composition
US6017742A (en) * 1994-07-20 2000-01-25 Nisshinbo Industries, Inc. Immobilization of biologically active substances on a carrier containing a carbodiimide group-containing polymer
US6121406A (en) * 1998-04-20 2000-09-19 Nisshinbo Industries, Inc. Mixture of hydrophilic dicyclohexylmethanecarbodiimide
US6204342B1 (en) 1997-08-27 2001-03-20 Reichhold Chemicals Thickening active H-containing resin with polycarbodiimide
US20030119954A1 (en) * 2001-12-13 2003-06-26 Brown Ward Thomas Crosslinkable composition
CN1120191C (en) * 1998-07-01 2003-09-03 巴斯福公司 Polycarbided diimine polymer and its use as inter-layer of adhesive layer in automobile paint
US6692802B1 (en) 1997-08-27 2004-02-17 Reichhold, Inc. Resins for lining surfaces
US20040158021A1 (en) * 2003-02-10 2004-08-12 Nitto Denko Corporation Polycarbodiimide having high index of refraction and production method thereof
US20040157992A1 (en) * 2003-02-04 2004-08-12 Nitto Denko Corporation Resin for the encapsulation of photosemiconductor element, photosemiconductor device comprising encapsulated optical semiconductor element, and process for producing the device
US20050142379A1 (en) * 2003-12-26 2005-06-30 Nitto Denko Corporation Electroluminescence device, planar light source and display using the same
US20060098066A1 (en) * 2003-11-12 2006-05-11 Bauer Richard D Inkjet ink, ink set and method of printing
US9957394B2 (en) 2016-09-07 2018-05-01 Ppg Industries Ohio, Inc. Methods for preparing powder coating compositions
US10058502B2 (en) 2015-12-31 2018-08-28 L'oreal Nail polish compositions

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4318979A1 (en) * 1993-06-08 1994-12-15 Basf Ag Carbodiimides and / or oligomeric polycarbodiimides based on 1,3-bis (1-methyl-1-isocyanatoethyl) benzene, a process for their preparation and their use as a hydrolysis stabilizer
EP0881243B1 (en) * 1997-05-19 2004-11-17 Nisshinbo Industries, Inc. Curing agent for powder coatings, powder coating composition comprising said curing agent, and powder coating film
EP0969029B1 (en) * 1998-06-05 2003-11-26 Basf Corporation Novel polycarbodiimide polymers and their use as adhesive intermediate layers in automotive coatings
AU2006316919B2 (en) 2005-11-28 2012-06-07 Sakata Inx Corp. Liquid developer
JP6055353B2 (en) * 2013-03-28 2016-12-27 日清紡ケミカル株式会社 Ester resin composition, method for producing ester resin composition, and molded article using ester resin
WO2024083487A1 (en) 2022-10-18 2024-04-25 Sabic Global Technologies B.V. Method of preparing a hydrostable thermoplastic composition
WO2024083484A1 (en) 2022-10-18 2024-04-25 Sabic Global Technologies B.V. Hydrostable thermoplastic composition

Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2853473A (en) * 1956-08-27 1958-09-23 Du Pont Production of carbodiimides
US2941983A (en) * 1957-05-07 1960-06-21 Du Pont Urethane-terminated polycarbodiimides
US2941966A (en) * 1956-08-27 1960-06-21 Du Pont Carbodiimide polymers
CA651629A (en) * 1962-11-06 W. Campbell Tod Carbodiimide polymers
US3426025A (en) * 1961-11-28 1969-02-04 Du Pont Catalysts for preparing carbodiimides
US3640966A (en) * 1968-01-25 1972-02-08 Bayer Ag Process for the preparation of polyisocyanates which contain a carbodiimide-isocyanate adduct
US3755242A (en) * 1972-04-10 1973-08-28 Minnesota Mining & Mfg Polycarbodiimide prepolymers
US3907780A (en) * 1973-01-15 1975-09-23 Ici Ltd Preparation of carbodiimide-containing isocyanates
US3929733A (en) * 1974-10-02 1975-12-30 Upjohn Co Polycarbodiimides from 4,4{40 -methylenebis(phenyl isocyanate) and certain carbocyclic monoisocyanates
US3960950A (en) * 1973-06-08 1976-06-01 Minnesota Mining And Manufacturing Company Process for carbodiiomide synthesis
US4014935A (en) * 1975-04-03 1977-03-29 Imperial Chemical Industries Limited Carbodiimides
US4066629A (en) * 1976-10-28 1978-01-03 Celanese Corporation Process for preparing carbodiimides utilizing a phosphonium salt catalyst
US4067820A (en) * 1975-02-01 1978-01-10 Bayer Aktiengesellschaft High molecular weight, insoluble carbodiimidization catalysts
US4088665A (en) * 1975-08-23 1978-05-09 Bayer Aktiengesellschaft Process for the partial carbodiimidization of organic isocyanates
US4105642A (en) * 1977-01-31 1978-08-08 The Upjohn Company Preparation of carbodiimide in presence of phospholene catalysts
US4105643A (en) * 1977-01-31 1978-08-08 The Upjohn Company Preparation of carbodiimide in presence of phospholene catalysts
US4148844A (en) * 1976-05-29 1979-04-10 Bayer Aktiengesellschaft Polymerization products containing polycarbodiimides and vinyl monomers
US4284730A (en) * 1980-02-07 1981-08-18 Basf Wyandotte Corporation Liquid carbodiimide- and uretonimine-isocyanurate-containing polyisocyanate compositions and microcellular foams made therefrom
US4294719A (en) * 1975-02-01 1981-10-13 Bayer Aktiengesellschaft Polyisocyanates which contain carbodiimide groups and which are stable in storage
US4344855A (en) * 1975-11-21 1982-08-17 Bayer Aktiengesellschaft Process for the production of polyisocyanates which contain carbodiimide groups and which are stable in storage
US4487964A (en) * 1983-02-24 1984-12-11 Union Carbide Corporation Method of making mixed aliphatic/aromatic polycarbodiimides
JPH02202906A (en) * 1989-02-01 1990-08-13 Mitsui Toatsu Chem Inc Production of polycarbodiimide
US5008363A (en) * 1990-03-23 1991-04-16 Union Carbide Chemicals And Plastics Technology Corporation Low temperature active aliphatic aromatic polycarbodiimides
US5100994A (en) * 1989-07-29 1992-03-31 Nisshinbo Industries, Inc. Hydrophilic polycarbodiimide polymer, pulp-like material consisting of said hydrophilic polycarbodiimide polymer, and process for producing said polymer or said material
EP0548815A2 (en) * 1991-12-26 1993-06-30 Nisshinbo Industries, Inc. Tetramethylxylylene carbodiimides
US5246993A (en) * 1991-08-09 1993-09-21 Basf Aktiengesellschaft Oligomeric carbodiimides
US5264518A (en) * 1991-07-03 1993-11-23 Nisshinbo Industries, Inc. Polycarbodiimide pulp and process for producing thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3643238C2 (en) * 1985-03-29 1989-08-03 Nisshinbo Industries, Inc., Tokio/Tokyo, Jp

Patent Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA651629A (en) * 1962-11-06 W. Campbell Tod Carbodiimide polymers
US2853473A (en) * 1956-08-27 1958-09-23 Du Pont Production of carbodiimides
US2941966A (en) * 1956-08-27 1960-06-21 Du Pont Carbodiimide polymers
US2941983A (en) * 1957-05-07 1960-06-21 Du Pont Urethane-terminated polycarbodiimides
US3426025A (en) * 1961-11-28 1969-02-04 Du Pont Catalysts for preparing carbodiimides
US3640966A (en) * 1968-01-25 1972-02-08 Bayer Ag Process for the preparation of polyisocyanates which contain a carbodiimide-isocyanate adduct
US3755242A (en) * 1972-04-10 1973-08-28 Minnesota Mining & Mfg Polycarbodiimide prepolymers
US3907780A (en) * 1973-01-15 1975-09-23 Ici Ltd Preparation of carbodiimide-containing isocyanates
US3960950A (en) * 1973-06-08 1976-06-01 Minnesota Mining And Manufacturing Company Process for carbodiiomide synthesis
US3929733A (en) * 1974-10-02 1975-12-30 Upjohn Co Polycarbodiimides from 4,4{40 -methylenebis(phenyl isocyanate) and certain carbocyclic monoisocyanates
US4067820A (en) * 1975-02-01 1978-01-10 Bayer Aktiengesellschaft High molecular weight, insoluble carbodiimidization catalysts
US4294719A (en) * 1975-02-01 1981-10-13 Bayer Aktiengesellschaft Polyisocyanates which contain carbodiimide groups and which are stable in storage
US4014935A (en) * 1975-04-03 1977-03-29 Imperial Chemical Industries Limited Carbodiimides
US4088665A (en) * 1975-08-23 1978-05-09 Bayer Aktiengesellschaft Process for the partial carbodiimidization of organic isocyanates
US4344855A (en) * 1975-11-21 1982-08-17 Bayer Aktiengesellschaft Process for the production of polyisocyanates which contain carbodiimide groups and which are stable in storage
US4148844A (en) * 1976-05-29 1979-04-10 Bayer Aktiengesellschaft Polymerization products containing polycarbodiimides and vinyl monomers
US4066629A (en) * 1976-10-28 1978-01-03 Celanese Corporation Process for preparing carbodiimides utilizing a phosphonium salt catalyst
US4105643A (en) * 1977-01-31 1978-08-08 The Upjohn Company Preparation of carbodiimide in presence of phospholene catalysts
US4105642A (en) * 1977-01-31 1978-08-08 The Upjohn Company Preparation of carbodiimide in presence of phospholene catalysts
US4284730A (en) * 1980-02-07 1981-08-18 Basf Wyandotte Corporation Liquid carbodiimide- and uretonimine-isocyanurate-containing polyisocyanate compositions and microcellular foams made therefrom
US4487964A (en) * 1983-02-24 1984-12-11 Union Carbide Corporation Method of making mixed aliphatic/aromatic polycarbodiimides
JPH02202906A (en) * 1989-02-01 1990-08-13 Mitsui Toatsu Chem Inc Production of polycarbodiimide
US5100994A (en) * 1989-07-29 1992-03-31 Nisshinbo Industries, Inc. Hydrophilic polycarbodiimide polymer, pulp-like material consisting of said hydrophilic polycarbodiimide polymer, and process for producing said polymer or said material
US5008363A (en) * 1990-03-23 1991-04-16 Union Carbide Chemicals And Plastics Technology Corporation Low temperature active aliphatic aromatic polycarbodiimides
US5264518A (en) * 1991-07-03 1993-11-23 Nisshinbo Industries, Inc. Polycarbodiimide pulp and process for producing thereof
US5246993A (en) * 1991-08-09 1993-09-21 Basf Aktiengesellschaft Oligomeric carbodiimides
EP0548815A2 (en) * 1991-12-26 1993-06-30 Nisshinbo Industries, Inc. Tetramethylxylylene carbodiimides

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Campbell et al; Carbodiimides. IV. High Polymers Containing the Carbodiimide Repeat Unit; vol. 28; Aug., 1963; pp. 2069 2075. *
Campbell et al; Carbodiimides. IV. High Polymers Containing the Carbodiimide Repeat Unit; vol. 28; Aug., 1963; pp. 2069-2075.

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5688875A (en) * 1994-06-10 1997-11-18 Nisshinbo Industries, Inc. Hydrophilic tetramethylxylylenecarbodiimide
US6017742A (en) * 1994-07-20 2000-01-25 Nisshinbo Industries, Inc. Immobilization of biologically active substances on a carrier containing a carbodiimide group-containing polymer
US6127029A (en) * 1994-08-11 2000-10-03 Nisshinbo Industries, Inc. Reinforcing material surface-treated with aqueous surface-treating agent, and composite material comprising said reinforcing material
US5958516A (en) * 1994-08-11 1999-09-28 Nisshinbo Industries, Inc. Method for surface treating reinforcing material with aqueous carbodiimide containing composition
US6127477A (en) * 1994-08-11 2000-10-03 Nisshinbo Industries, Inc. Method for surface treating reinforcing material with an aqueous surface-treating agent comprising a carbodiimide compound
EP0780440A2 (en) 1995-12-22 1997-06-25 Rohm And Haas Company Crosslinkable compositions with an aliphatil polycarbodiimide
US6194522B1 (en) 1995-12-22 2001-02-27 Rohm And Haas Company Crosslinkable compositions
US5912290A (en) * 1996-02-06 1999-06-15 Nisshinbo Industries, Inc. Hydrolysis stabilizer for ester group-containing resin
US5925409A (en) * 1997-08-27 1999-07-20 Reichhold, Inc. Resins for lining surfaces
US6204342B1 (en) 1997-08-27 2001-03-20 Reichhold Chemicals Thickening active H-containing resin with polycarbodiimide
US20040053062A1 (en) * 1997-08-27 2004-03-18 Hildeberto Nava Resins for lining surfaces
US6692802B1 (en) 1997-08-27 2004-02-17 Reichhold, Inc. Resins for lining surfaces
US6121406A (en) * 1998-04-20 2000-09-19 Nisshinbo Industries, Inc. Mixture of hydrophilic dicyclohexylmethanecarbodiimide
CN1120191C (en) * 1998-07-01 2003-09-03 巴斯福公司 Polycarbided diimine polymer and its use as inter-layer of adhesive layer in automobile paint
US20030119954A1 (en) * 2001-12-13 2003-06-26 Brown Ward Thomas Crosslinkable composition
US7009006B2 (en) 2001-12-13 2006-03-07 Rohm And Haas Company Crosslinkable composition
US20040157992A1 (en) * 2003-02-04 2004-08-12 Nitto Denko Corporation Resin for the encapsulation of photosemiconductor element, photosemiconductor device comprising encapsulated optical semiconductor element, and process for producing the device
US20040158021A1 (en) * 2003-02-10 2004-08-12 Nitto Denko Corporation Polycarbodiimide having high index of refraction and production method thereof
US20060098066A1 (en) * 2003-11-12 2006-05-11 Bauer Richard D Inkjet ink, ink set and method of printing
US7425062B2 (en) 2003-11-12 2008-09-16 E.I. Du Pont De Nemours And Company Inkjet ink, ink set and method of printing
US20050142379A1 (en) * 2003-12-26 2005-06-30 Nitto Denko Corporation Electroluminescence device, planar light source and display using the same
US7722965B2 (en) 2003-12-26 2010-05-25 Nitto Denko Corporation Electroluminescence device, planar light source and display using the same
US10058502B2 (en) 2015-12-31 2018-08-28 L'oreal Nail polish compositions
US9957394B2 (en) 2016-09-07 2018-05-01 Ppg Industries Ohio, Inc. Methods for preparing powder coating compositions

Also Published As

Publication number Publication date
DE69305282D1 (en) 1996-11-14
CA2103625C (en) 2002-12-10
JP3188959B2 (en) 2001-07-16
JPH0656950A (en) 1994-03-01
EP0582983B1 (en) 1996-10-09
DE69305282T2 (en) 1997-06-26
EP0582983A1 (en) 1994-02-16
CA2103625A1 (en) 1994-02-11

Similar Documents

Publication Publication Date Title
US5373080A (en) Process for producing polycarbodiimide resin
US5360933A (en) Tetramethylxylylene carbodiimide
CA2069384A1 (en) A process for the preparation of liquid storable organic isocyanates containing carbodimide and/or uretone imine groups and their use for the preparation of polyurethane plastics
EP0671426A1 (en) Modified blends of (cyclo)aliphatic polyisocyanates, process for their preparation and their use
EP0044421A1 (en) Di- and oligo-1,2,4-triazolidine-3,5 diones and processes for their preparation
DE69311633D1 (en) Storage stable polyurea coating compositions
DE19813352A1 (en) Malonic ester-blocked polyisocyanates with formaldehyde against thermal yellowing
US5416184A (en) High-molecular weight polycarbodiimide solution and methods for producing the same
CA2184239A1 (en) Polycyclic iminooxadiazinediones, their preparation and use
US5338794A (en) Process for producing solution of high-molecular weight polycarbodiimide
US7034101B2 (en) Polycarbodiimide copolymer and production method thereof
BR112021008046A2 (en) method for removing organic monoisocyanates from an organic solvent, and, manufacturing process for polymeric mdi and/or mdi.
JPH1036469A (en) Thermosetting resin
EP4036140A1 (en) Modified polycarbodiimide compound having hydrophilic group
US4923952A (en) Monoformylated 3,3'-diaminodipropylamines, a process for their production and their use
US5130466A (en) Diisocyanate, a process for its production and its use
JPH08333430A (en) Production of high-molecular-weight polycarbodiimide solution
US4320069A (en) Oxazoline stabilized diphenylmethane diisocyanate-polymethylene polyphenyl isocyanate compositions
KR940010279B1 (en) Process for the preparation of 4,4-methylene-bis-(n-phenyl arkyl carbamete) by condensation n-phenyl arkyl carbamate
EP0002444B1 (en) Process for preparing hydantoins and compounds obtainable by this process
WO2024124426A1 (en) Isophorone diisocyanate composition and blocked product thereof
JPH0841155A (en) Moisture-curable polyurethane composition
EP0141446B1 (en) Process for the preparation of an isocyanurate compound containing isocyanate groups
Matsui et al. Side reactions of phenylisocyanate in N, N‐dimethylacetamide
JP2000204157A (en) Polycarbodiimide and its production

Legal Events

Date Code Title Description
AS Assignment

Owner name: NISSHINBO INDUSTRIES, INC.

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:IMASHIRO, YASUO;TAKAHASHI, IKUO;REEL/FRAME:006657/0379

Effective date: 19930727

STCF Information on status: patent grant

Free format text: PATENTED CASE

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 12